EP1059947B1 - Polymerisats absorbant l'eau, sous forme de mousse, reticules, leur procede de production et leur utilisation - Google Patents

Polymerisats absorbant l'eau, sous forme de mousse, reticules, leur procede de production et leur utilisation Download PDF

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EP1059947B1
EP1059947B1 EP99913215A EP99913215A EP1059947B1 EP 1059947 B1 EP1059947 B1 EP 1059947B1 EP 99913215 A EP99913215 A EP 99913215A EP 99913215 A EP99913215 A EP 99913215A EP 1059947 B1 EP1059947 B1 EP 1059947B1
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Prior art keywords
foam
water
mol
expanded
polymerization
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German (de)
English (en)
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EP1059947A1 (fr
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Hans-Joachim HÄHNLE
Ulrich Schröder
Martin Beck
Wolfgang Heider
Gunnar Schornick
Thomas Anstock
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the invention relates to water-absorbent, foam-like, cross-linked Polymers, processes for their preparation and their Use in sanitary ware used to absorb body fluids and in dressings to cover wounds be used.
  • Water-absorbing, crosslinked polymers are called superabsorbents or superabsorbent polymers because they are in are able to multiply their own weight in aqueous Absorb liquids to form hydrogels.
  • superabsorbents are used in diapers for absorption, for example used by urine.
  • the superabsorbers have the property the absorbed liquid even under mechanical stress withhold.
  • a foam falling under category (1) made from a mixture that on the one hand components for the formation of a polyurethane foam and on the other hand polymerizable Monomers, a crosslinker and a polymerization initiator contains for the production of a super absorber. From one such mixture is in a polycondensation reaction from the Polyurethane components are formed by the foam, which by Polymerization of the superabsorbers in the form of monomers an interpenetrating network, cf. US-A-4 725 628, US-A-4 725 629 and US-A-4 731 391.
  • the category (2) of foams includes, for example Products obtained by making a pre-made one Super absorber in an extruder with a polyhydroxy compound and a blowing agent at an elevated temperature. At the Pressing the mixture out of the extruder forms the foam. Methods of this type are described, for example, in US Pat. No. 4,394,930, US-A-4 415 388 and GB-A-2 136 813.
  • US-A-4 529 739 and US-A-4 649 154 disclose methods of manufacture of foams known to be a water-swellable, COOH group foaming load-bearing material with a blowing agent that in a neutralization reaction with the COOH groups of the polymer releases the propellant.
  • EP-A-04 21 264 describes the production of foam-like superabsorbents known, wherein an aqueous monomer mixture, the contains an oil phase emulsified, polymerized.
  • the oil works here as a placeholder for the later pores of the foam and will after completion of the polymerization when drying the foam Material removed by evaporation.
  • hydrophilic polymers e.g. Polysodium acrylate in the presence of crosslinking agents such as polyepoxides and blowing agents by heating to a foam Super absorber can process.
  • an absorber element made of a composite material is known from the elements made of a superabsorbent foam at such intervals a carrier are arranged so that the elements in their swollen state Touch circumferences.
  • the superabsorbent foam is made by (I) foaming one polymerizable aqueous mixture, the essential components of acid groups contains containing ethylenically unsaturated monomers, crosslinkers and surfactants, according to Whipped foam method and (II) polymerizing the foamed mixture to form of a foam-shaped hydrogel.
  • the water content of the show material will optionally adjusted to 1 to 60% by weight.
  • foam-shaped superabsorbents Working method known in which one carbonates, bicarbonates or carbon dioxide as a blowing agent to form a mixture of carboxyl groups bearing monomers, crosslinking agent and polymerization initiator adds, simultaneously with the addition of the blowing agent or shortly afterwards the polymerization of the monomers started becomes.
  • the superabsorbent receives through this in the neutralization reaction carbon dioxide formed a foam structure, cf. EP-A-2 954 438 and US-A-4 808 637.
  • WO-A-95/02002 known method is a foam-shaped super absorber afterwards production with one and more for subsequent Surface crosslinked reactive compounds and heated to a temperature of 100 to 300 ° C.
  • the water content of the foam hydrogel set to 1 to 45 wt .-%.
  • the so available foam-like polymers are used in sanitary articles, e.g. used to absorb body fluids.
  • JP-A-08073507 describes soft and flexible superabsorbent films wrote that are produced by the fact that an aqueous Acrylate solution, which is partially neutralized by an alkanolamine is polymerized in the presence of a crosslinking agent.
  • the films obtained are described as soft and flexible, however, no information is given under which climatic conditions the flexibility is maintained. In particular, there is no information for elevated or lowered temperatures available.
  • these products have several serious ones Disadvantages. So is their recording speed for the use in hygiene articles completely inadequate and too their absorption capacity is still in need of improvement. henceforth the films show a pronounced restriction of handling Stickiness.
  • Super absorber foams based on acid group bearing crosslinked polymers e.g. according to the above References DE-A-19540951, DE-A-19607551 or W-A-094/22502 can be produced by setting a defined Moisture content of approx. 25% can be obtained softly and flexibly. Even if additional flexibility measures, such as in described in the above patents, is nevertheless in usually a moisture content of at least 20% is necessary. The Flexibility through such a high water content brings the Disadvantage that they are not stable at low air humidity is. At a relative humidity below 50%, the begins Drying out foam increasingly loses its flexibility. Likewise, the flexibility of the foam decreases at temperatures below 5 ° C quickly.
  • the invention has for its object a superabsorbent To provide foam that is relevant to the application Conditions, e.g. at temperatures between ⁇ 15 ° C and + 50 ° C and a relative humidity of 20 to 95%, constantly flexible is and at the same time the other disadvantages described overcomes.
  • a polymerizable aqueous mixture is processed into a foam which is stable in processing and can be shaped in any way.
  • the polymerizable aqueous mixture contains as components (a) monoethylenically unsaturated monomers containing acid groups, which are optionally neutralized.
  • monomers are, for example, monoethylenically unsaturated C 3 -C 25 -carboxylic acids or anhydrides, for example acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
  • Monoethylenically unsaturated monomers also come as group (a) monomers Sulfonic acids, for example vinyl sulfonic acid, Allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, Sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropyl sulfonic acid, Vinyl phosphoric acid, allylphosphonic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • the monomers can be used alone or in Mixing with each other in the manufacture of the superabsorbent Foams are used.
  • Preferred monomers used Group (a) are acrylic acid, methacrylic acid, vinyl sulfonic acid, Acrylamidopropanesulfonic acid or mixtures of these acids, e.g. Mixtures of acrylic acid and methacrylic acid, mixtures of Acrylic acid and acrylamidopropanesulfonic acid or mixtures of Acrylic acid and vinyl sulfonic acid.
  • the monomers are optionally neutralized.
  • neutralization one uses, for example, alkali metal bases or ammonia or amines.
  • Sodium hydroxide solution is preferably used for neutralization or potash lye.
  • neutralization can also be done with the help of sodium carbonate, sodium hydrogen carbonate, potassium carbonate or Potassium bicarbonate or other carbonates or bicarbonates or ammonia.
  • the acid groups of the Monomers are preferably at least 15 to 40 mol% with at least one of the bases given above neutralized.
  • the monomers (a) are neutralized with at least 20 mol% tertiary alkanolamines.
  • An embodiment is particularly preferred in which you have at least 40 mol% of the acid groups containing monomers (a) with tertiary alkanolamines neutralized.
  • the monomers (a) can additionally be processed with the bases described above, in particular NaOH or ammonia, neutralize up to 100%, for example.
  • the degree of neutralization of the monomers (a) containing acid groups with tertiary alkanolamines are 20 to 95, preferably 30 to 70 mol%.
  • tertiary Amines are triethanolamine, methyldiethanolamine, dimethylaminodiglycol, Dimethylethanolamine and N, N, N ', N'-tetra (hydroxyethyl) ethylenediamine. Another embodiment of the invention The procedure is described below.
  • the polymerizable aqueous mixture can optionally contain monomers of group (b).
  • monomers of group (b) This is to be understood as meaning other monoethylenically unsaturated monomers which can be copolymerized with the monomers (a) and (c).
  • monomers of group (b) include, for example, the amides and nitriles of monoethylenically unsaturated carboxylic acids, for example acrylamide, methacrylamide and N-vinylformamide, acrylonitrile and methacrylonitrile, dialkyldiallylammonium halides, such as dimethyldiallylammonium chloride, allylpiperidiniumbromide and N-vinylolimidolol, such as vinylidolimidolazole N-vinylimidazolines such as N-vinylimidazoline, 1-vinyl-2-methylimidazoline, 1-vinyl-2-ethylimidazoline or 1-vinyl-2
  • Dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate are also suitable.
  • the basic esters are preferably used in quaternized form or as a salt.
  • Suitable compounds of group (b) are, for example, vinyl esters of saturated C 1 -C 4 -carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ethers with at least 2 C atoms in the alkyl group, such as ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C 3 to C 6 carboxylic acids, for example esters of monohydric C 1 to C 18 alcohols and acrylic acid, methacrylic acid or maleic acid, half-esters of maleic acid, for example monomethyl maleate and hydroxyalkyl esters of the monoethylenically unsaturated carboxylic acids mentioned, for example 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate Hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate, N-vinyl lactams such as N-vin
  • Suitable monomers of group (b) are alkyl-substituted styrenes such as ethylstyrene or tert. Butylstyrene.
  • the monomers of group (b) can also be used in a mixture in the copolymerization with the other monomers, for example mixtures of vinyl acetate and 2-hydroxyethyl acrylate in any ratio.
  • the monomers of group (c) have at least 2 ethylenically unsaturated Double bonds.
  • Polymerization reactions are usually used as crosslinkers are, N, N'-methylene bisacrylamide, polyethylene glycol diacrylates and polyethylene glycol dimethacrylates, each of which Polyethylene glycols with a molecular weight of 106 to 8500, preferably 400 to 2000, derived, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, Butanediol diacrylate, hexanediol diacrylate, Hexanediol dimethacrylate, diacrylates and dimethacrylates of block copolymers from ethylene oxide and propylene oxide, twice or triple esterified with acrylic acid or methacrylic acid Alcohols, such as glycerol or pentaerythritol, triallylamine, Tetralylethylenedi
  • Water-soluble crosslinking agents are preferably used, e.g. N, N'-methylene bisacrylamide, polyethylene glycol diacrylates and Polyethylene glycol dimethacrylates, which differ from addition products from 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol derive vinyl ethers from addition products from 2 to 400 mol Ethylene oxide with 1 mole of a diol or polyol, ethylene glycol diacrylate, Ethylene glycol dimethacrylate or triacrylates and trimethacrylates addition products of 6 to 20 moles of ethylene oxide to one mole of glycerol, pentaerythritol triallyl ether and / or divinyl urea.
  • crosslinkers are compounds which have at least a polymerizable ethylenically unsaturated group and contain at least one further functional group.
  • the functional Group of these crosslinkers must be able to use the functional groups, essentially the carboxyl groups or React sulfonic acid groups of the monomers (a).
  • suitable functional groups are, for example, hydroxyl, amino, Epoxy and aziridino groups.
  • crosslinkers are those compounds which carry at least two functional groups which are linked with carboxyl and sulfonic acid groups of the monomers used Group (a) can react.
  • the appropriate functional groups have already been mentioned above, i.e. Hydroxyl, amino, epoxy, isocyanate, Ester, amide and aziridino groups.
  • crosslinkers examples are ethylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, Propylene glycol, polypropylene glycol, block copolymers from ethylene oxide and propylene oxide, sorbitan fatty acid esters, ethoxylated Sorbitan fatty acid esters, trimethylolpropane, pentaerythritol, Polyvinyl alcohol, sorbitol, polyglycidyl ethers such as ethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, Glycerol polyglycidyl ether, diglycerol polyglycidyl ether, Polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, Propylene glycol digly
  • crosslinkers are polyvalent metal ions, which in are able to develop ionic networks.
  • examples for such crosslinkers are magnesium, calcium, barium and aluminum ions.
  • a preferred crosslinker of this type is sodium aluminate. These crosslinkers are used, for example, as hydroxides, Carbonates or hydrogen carbonates of the aqueous polymerizable Solution added.
  • crosslinkers are multifunctional bases that are also able to form ionic networks, for example polyamines or their quaternized salts.
  • polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, Tetraethylene pentamine, pentaethylene hexamine and polyethyleneimines as well as polyvinylamines with molecular weights of up to 4,000,000th
  • two different crosslinkers are used, one of which is water-soluble and the other is water-insoluble.
  • the hydrophilic crosslinker which is soluble in the aqueous phase of the reaction mixture is, in a conventional manner, causes a relatively uniform Crosslinking of the resulting polymer, as is the case during production of a super absorber is common.
  • the hydrophobic crosslinker which in the polymerizable aqueous mixture insoluble or only therein is of limited solubility, accumulates in the surfactant boundary layer between the gas phase and the polymerizable aqueous phase on. This will make the surface in the subsequent polymerization of the foam is more networked than the inner part of the SAP hydrogel.
  • Products with a core-shell structure are homogeneous cross-linked samples with regard to the absorption speed, distribution effect and gel stability significantly improved properties.
  • polyvalent metal ions all are above described water-insoluble crosslinker
  • the different Groups can be assigned suitable to using foams to produce a core-shell structure, i.e. Foams where the entire surface is more networked than the one below Layer referred to above as the core layer.
  • Especially preferred hydrophobic crosslinkers are diacrylates or dimethacrylates or divinyl ethers of alkanediols with 2 to 25 C atoms (branched, linear, with any arrangement of the OH groups) like e.g.
  • Suitable hydrophilic crosslinkers are, for example, N, N'-methylenebisacrylamide, polyethylene glycol diacrylates or dimethacrylates with a molecular weight M N of 200 to 4000, dinvinylurea, triallylamine, diacrylates or dimethacrylates of addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol or that Triacrylate of an addition product of 20 moles of ethylene oxide with 1 mole of glycerol and vinyl ether of addition products of 2 to 400 moles of ethylene oxide with 1 mole of a diol or polyol.
  • the monomers of group (a) are in the polymerizable aqueous Mixture for example in amounts of 10 to 90 and preferably Contain 20 to 85 wt .-%.
  • the monomers of group (b) are only used if necessary to modify the superabsorbent foams used and can be used in amounts up to 50, preferably in amounts up to 20 wt .-% in the polymerizable aqueous Mixture may be included.
  • the crosslinkers (c) are in the reaction mixture for example from 0.001 to 8 and preferably from 0.01 and 5% by weight.
  • All of the polymerization initiators can be used under the polymerization conditions compounds that break down into radicals e.g. Peroxides, hydroperoxides. hydrogen peroxide, Persulfates, azo compounds and the so-called redox catalysts.
  • the use of water-soluble initiators is preferred. In some cases it is advantageous to mix different ones
  • To use polymerization initiators e.g. Mixtures of Hydrogen peroxide and sodium or potassium peroxydisulfate. Mixtures of hydrogen peroxide and sodium peroxydisulfate can can be used in any ratio.
  • suitable organic peroxides are, for example, acetylacetone peroxide, Methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, di- (2-ethylhexyl) peroxidicarbonate, Dicyclohexylperoxydicarbonate, di- (4-tert-butylcyclohexyl) peroxidicarbonate, Dimyristil peroxidicarbonate, diacetyl peroxydicarbonate, Allyl perester,
  • Particularly suitable polymerization initiators are water-soluble Azostarter, e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis [2- (2'-imidazolin-2-yl) propane] dihydrochloride and 4,4'-azobis (4-cyanovaleric acid).
  • the polymerization initiators mentioned are in customary amounts used, e.g. in amounts of 0.01 to 5, preferably 0.1 up to 2.0% by weight, based on the monomers to be polymerized.
  • Redox catalysts are also suitable as initiators.
  • the redox catalysts contain at least one of the above-mentioned per compounds as the oxidizing component and as reducing component, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts such as iron II ions or silver ions or sodium hydroxymethyl sulfoxylate.
  • Ascorbic acid or sodium sulfite is preferably used as the reducing component of the redox catalyst.
  • initiators are usually used Photoinitiators. This can be, for example so-called ⁇ -splitters, H-abstracting systems or azides act.
  • initiators are benzophenone derivatives such as Michlers ketone, phenanthrene derivatives, fluorene derivatives, Anthraquinone derivatives, thioxanone derivatives, coumarin derivatives, Benzoin ethers and their derivatives, azo compounds such as those above radical generator, substituted hexaarylbisimidazoles or Acylphosphine.
  • azides examples include: 2- (N, N-dimethylamino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl-4-azidonaphthylketon, 2- (N, N-dimethylamino) ethyl-4-azidobenzoate, 5-azido-1-naphthyl-2 '- (N, N-dimethylamino) ethyl sulfone, N- (4-sulfonyl azidophenyl) maleimide, N-acetyl-4-sulfonylazidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p-azidobenzoic acid, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (p-azido
  • the polymerizable aqueous mixtures contain as a component (e) 0.1 to 20% by weight of at least one surfactant.
  • the surfactants are for the production and stabilization of the foam of vitally important.
  • nonionic surfactants are Addition products of alkylene oxides, especially ethylene oxide, Propylene oxide and / or butylene oxide over alcohols, amines, phenols, Naphthols or carboxylic acids.
  • surfactants Addition products of ethylene oxide and / or propylene oxide at least Alcohols containing 10 carbon atoms, the addition products per mole of alcohol 3 to 200 moles of ethylene oxide and / or Contained propylene oxide.
  • the addition products included the alkylene oxide units in the form of blocks or in statistical Distribution.
  • nonionic surfactants are Addition products of 7 moles of ethylene oxide with 1 mole of tallow fatty alcohol.
  • Reaction products of 9 moles of ethylene oxide with 1 mole of tallow fatty alcohol and addition products of 80 moles of ethylene oxide with 1 mole of tallow fatty alcohol consist of reaction products of oxo alcohols or Ziegler alcohols with 5 to 12 moles of ethylene oxide per mole of alcohol, in particular with 7 moles of ethylene oxide.
  • Further commercially available nonionic surfactants are obtained by ethoxylating castor oil. For example, 12 to 80 moles of ethylene oxide are added per mole of castor oil.
  • reaction products of 18 mol ethylene oxide with 1 mol tallow fatty alcohol are, for example, the reaction products of 18 mol ethylene oxide with 1 mol tallow fatty alcohol, the addition products of 10 mol ethylene oxide with 1 mol of a C 13 / C 15 oxo alcohol, or the reaction products with 7 to 8 mol ethylene oxide with 1 mol of a C 13 / C 15 oxo alcohol.
  • suitable nonionic surfactants are phenol alkoxylates such as p-tert-butylphenol, which has been reacted with 9 mol of ethylene oxide, or methyl ether of reaction products from 1 mol of a C 12 -C 18 alcohol and 7.5 mol of ethylene oxide.
  • the nonionic surfactants described above can be converted into the corresponding sulfuric acid semiesters, for example by esterification with sulfuric acid.
  • the sulfuric acid half-esters are used in the form of the alkali metal or ammonium salts as anionic surfactants.
  • Suitable anionic surfactants are, for example, alkali metal or ammonium salts of sulfuric acid semiesters of addition products of ethylene oxide and / or propylene oxide with fatty alcohols, alkali metal or ammonium salts of alkylbenzenesulfonic acid or of alkylphenol ether sulfates. Products of the type mentioned are commercially available.
  • the sodium salt of a sulfuric acid half ester of a C 13 / C 15 oxo alcohol reacted with 106 moles of ethylene oxide, the triethanolamine salt of dodecylbenzenesulfonic acid, the sodium salt of alkylphenol ether sulfates and the sodium salt of the sulfuric acid half ester of a reaction product of 106 moles of ethylene oxide with 1 mole of tallow fatty alcohol with 1 mole of tallow fat.
  • Suitable anionic surfactants are Schwefelbachsteder of C 13 / C 15 oxo alcohols, paraffin sulfonic acids, such as C 15 alkyl sulfonate, alkyl-substituted benzene sulfonic acids and alkyl-substituted naphthalenesulfonic acids such as dodecylbenzenesulfonic acid, and di-n-butylnaphthalenesulfonic acid and Fetcalkoholphosphate such as C 15 / C 18 -Fettalkoholphosphat.
  • paraffin sulfonic acids such as C 15 alkyl sulfonate, alkyl-substituted benzene sulfonic acids and alkyl-substituted naphthalenesulfonic acids such as dodecylbenzenesulfonic acid, and di-n-butylnaphthalenesulfonic acid and Fetcalk
  • the polymerizable aqueous mixture can contain combinations of a nonionic surfactant and an anionic surfactant or combinations of nonionic surfactants or combinations of anionic surfactants.
  • Cationic surfactants are also suitable. Examples of these are the reaction products of 6.5 mol of ethylene oxide with 1 mol of oleylamine, distearyldimethylammonium chloride, lauryltrimethylammonium chloride, cetylpyridinium bromide and stearic acid triethanolamine quaternized with dimethyl sulfate, which is preferably used as a cationic surfactant, quaternized with dimethyl sulfate.
  • the surfactant content of the polymerizable aqueous mixture is 0.1 to 20, preferably 0.5 to 10 wt .-%. In most cases the polymerizable aqueous mixtures have a surfactant content from 1.5 to 8% by weight.
  • the polymerizable aqueous mixtures can be used as a component (f) optionally contain at least one solubilizer.
  • solubilizers are understood to mean water-miscible organic solvents e.g. Alcohols, glycols, polyethylene glycols or monoethers derived therefrom, the monoethers having no double bonds contained in the molecule.
  • Suitable ethers are methyl glycol, Butyl glycol, butyl diglycol, methyl diglycol, butyl triglycol, 3-ethoxy-1-propanol and glycerol monomethyl ether.
  • the polymerizable aqueous mixtures contain 0 to 50% by weight of at least one solubilizer. In case of intermediaries are used, their content is in the polymerizable aqueous mixture preferably up to 25 wt .-%.
  • the polymerizable aqueous mixture can, if appropriate, thickeners, Foam stabilizers, polymerization regulators, fillers and contain cell nucleating agents.
  • thickeners to optimize the foam structure and improve the Foam stability used. It is achieved that the foam shrinks only slightly during the polymerization.
  • a thickener come all known natural and synthetic Polymers considered that have the viscosity of an aqueous Systems increase significantly. This can be water-swellable or water-soluble synthetic and natural polymers. Powdered superabsorbents are also suitable as thickeners.
  • a detailed overview of thickeners can be found, for example in the publications by R.Y. Lochhead and W.R.
  • Possible water swellable or water-soluble thickeners are high molecular weight Polymers of the acid groups described above under (a) monoethylenically unsaturated monomers.
  • Such thickeners are, for example, high molecular weight homopolymers of Acrylic acid and / or methacrylic acid or slightly cross-linked Copolymers of acrylic acid and / or methacrylic acid and one Compound containing at least 2 ethylenically unsaturated double bonds contains, e.g. Butanediol. They are also suitable high molecular weight polymers of acrylamide and methacrylamide or Copolymers of acrylic acid and acrylamide with molecular weights of more than 1 million.
  • copolymers are used as thickeners known.
  • high molecular weight polyethylene glycols or Copolymers of ethylene glycol and propylene glycol as well as high molecular weight Polysaccharides such as starch, guar gum, locust bean gum or derivatives of natural products such as carboxymethyl cellulose Hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose and cellulose mixed ethers are known thickeners.
  • thickeners are water-insoluble products, such as finely divided silicon dioxide, pyrogenic silicas, Precipitated silicas in hydrophilic or hydrophobic modifications, Zeolites, titanium dioxide, cellulose powder, or others from Superabsorbents different finely divided powders from cross-linked Polymers.
  • the polymerizable aqueous mixtures can contain the thickener in quantities of up to 30% by weight. If such Thickeners are used at all, they are in quantities from 0.1, preferably 0.5 to 20 wt .-% in the polymerizable contain aqueous mixture.
  • Hydrocarbons with at least 5 carbon atoms in the molecule to the add aqueous reaction mixture.
  • Suitable hydrocarbons are, for example, pentane, hexane, cyclohexane, heptane, octane, Isooctane, decane and dodecane.
  • the aliphatic in question Hydrocarbons can be straight chain, branched or be cyclical and have a boiling temperature that is above the Temperature of the aqueous mixture during foaming.
  • the Aliphatic hydrocarbons increase the life of the still unpolymerized foamed aqueous reaction mixture. This makes the handling of the not yet polymerized foams facilitated and increased process reliability.
  • the hydrocarbons are in amounts of 0 to 10 wt .-%, based on the polymerizable aqueous mixture used. In case of use are preferably present in the aqueous mixture Quantities 0.1 to 5% by weight.
  • a polymerization regulator or a mixture of several polymerization regulators add.
  • Suitable polymerization regulators are for example formic acid, thio compounds such as 2-mercaptoethanol, Mercaptopropanol, mercaptobutanol, dodecyl mercaptan, Thioglycolic acid or amines such as triethylamine, morpholine or Piperidine.
  • the amounts of polymerization regulator can be up to 10% by weight, based on the monomers used. If polymerization regulators are used, they are preferably used 0.1 to 5 wt .-%, based on the monomers.
  • Foam-like, crosslinked polymers are used in a first Process step the polymerizable aqueous described above Mixture foamed.
  • a gas inert to radicals in the form of fine bubbles dispersed in such a way that a foam forms.
  • the registration of gas bubbles in the monomer mixture succeeds, for example with the help of beating, shaking, stirring or whipping devices. It is also possible to produce such foams by that gases flow out of a liquid-covered opening or by taking advantage of turbulence in Currents.
  • the formation of fins can also Wires or sieves can be used for this purpose.
  • the foam is produced separately from the polymerization.
  • the polymerizable aqueous mixture can For example, be foamed in technical equipment that known for the production of urea-formaldehyde foams are, cf. Frisch and Saunders, Polymeric Foams Part II, p. 679 ff (1973). Foaming the polymerizable aqueous mixture can in the simplest case in the laboratory in a conventional Food processor, which is equipped with a whisk.
  • the Whipped foam is preferably produced in an inert gas atmosphere carried out. Examples of inert gases are nitrogen, Noble gases or carbon dioxide can be used. To make the Foam, all components of the reaction mixture are combined.
  • the temperatures of the polymerizable aqueous mixture are in the range of -10 to 100 during the foaming process, preferably 0 to + 50 ° C. In any case, when creating foam Temperatures applied below the boiling point of Components of the polymerizable aqueous mixture are.
  • the Foam can also be generated under increased pressure, e.g. at 1.5 to 25 bar. However, preference is given to atmospheric pressure worked.
  • foams according to the invention Compared to the previously known processes for the production of Foam-shaped super absorbers is a major advantage of the Production of such foams according to the invention can be seen in that one in the first stage of the process of the invention receives foamed, polymerizable aqueous mixtures that over a longer period, e.g. are stable for up to 6 hours, so that they can be handled easily, for example.
  • the not yet polymerized foam-like mixtures can for example for the subsequent polymerization into a suitable one Form to be brought up for a specific application to produce the desired shaped body.
  • the shape of the foamed polymerizable aqueous mixture possibly waste foam can be easily returned to the process become.
  • the foamed polymerizable material can for example in the desired strength to a temporary one Backing material, advantageously with a non-stick coating is equipped to be applied.
  • a non-stick coating is equipped to be applied.
  • One can for example, scrape the foam onto a surface.
  • a another option is to make the polymerizable foam fill aqueous mixture into molds that are also non-stick coated and polymerize the foam in it.
  • the foamed polymerizable aqueous mixture has a long life
  • This mixture is also suitable for production of composite materials.
  • the after polymerizable foam produced in the production of whipped foam be applied to a permanent carrier material, e.g. Films made of polymers (e.g. films made of polyethylene, polypropylene or polyamide) or metals, fleeces, fluff, tissues, fabrics, natural or synthetic fibers, or on other foams. at manufacturing composite materials may also be advantageous to shape the polymerizable foam of certain structures or in different layer thicknesses to apply to a carrier material.
  • the first stage available foamed polymerizable aqueous Mixture can also be molded into large blocks and polymerized become. The blocks can become smaller after polymerization Shaped bodies are cut or sawn.
  • You can also get sandwich-like Create structures by using a foamed polymerizable applies aqueous mixture to a base that foam-like layer with a foil, fleeces, tissues, fabrics, Fibers or other foams, if necessary, from another Material as the underlay used initially and covers again Applies foam and if necessary with another Foil, fleeces, tissues, fabrics, fibers or other foams covers.
  • the network is then in the second stage of the process Subjected to polymerization. However, you can also make sandwiches Create structures with additional foam layers.
  • the polymerization takes place in superabsorbent foams the foamed polymerizable aqueous mixture.
  • To the temperature of the foamed polymerizable to increase aqueous mixture can all be done in technology Use usual methods, for example the foam with heatable Contact plates, exposure to infrared radiation on the polymerizable foam or heating with the help of Microwaves.
  • Foam layers according to the invention with a layer thickness up to about 1 millimeter, for example by one-sided heating or in particular by one-sided Irradiate her.
  • the heating of the polymerizable foamed material with Using a microwave is particularly advantageous because of this Ways a relatively uniform heating can be achieved.
  • the polymerization takes place, for example, at temperatures from 20 to 180, preferably in the range from 20 to 100 ° C.
  • Foam layers of medium thickness i.e. with a thickness in the range of about 1 millimeter to about 2 centimeters, e.g. from about 2 millimeters to about 1 centimeter, is preferably made in the following way: Instead of polymerizing only one surface to initiate, you initiate bilateral initiation, by placing a layer of the foam according to the invention in a two-sided heat treatment and / or irradiation with light exposes.
  • the treatment of both surfaces of the foam layer can according to the invention synchronously or in any chronological order occur asynchronously or at different times.
  • the heat treatment is expediently carried out by contact heating and the carrier material used for this is usually opaque is the two-sided polymerization initiation most conveniently by contact heating a partial area and, for example simultaneous, irradiation of the opposite partial area carried out.
  • This process variant as well as the bilateral Contact heaters are particularly suitable for the production of Composite materials.
  • the heat treatment takes place during the two-sided polymerization initiation usually in a range from about 50 to about 200 ° C, preferably at about 80 to about 160 ° C. Typical contact times are about 0.5 to about 25 minutes per partial area the foam layer, preferably at about 2 to about 15 minutes.
  • Light from the is preferably used for the irradiation UV / VIS range, i.e. Light from the ultraviolet or visible Range of the spectrum, e.g. Light with a wavelength in the Range from approximately greater than 200 nm to approximately 750 nm, for example about 250 nm to about 700 nm, such as UV-A radiation of the wavelength 315 to 400 nm.
  • the duration of the irradiation can also be in the Range from about 0.1 to about 25 minutes, preferably about 0.5 to 10 minutes, depending on the partial area of the foam layer.
  • Time intervals can e.g. follow each other in time. For example can e.g. 3 minutes warming the first Partial area e.g. 2 minutes of exposure to the opposite follow the second section. This may apply e.g. 2 minute heat treatment of the first and / or the Connect the second section. This rhythm of treatment can if necessary while maintaining or changing the Repeat the selected time interval one or more times.
  • the selected time intervals can also overlap. For example you can only use part of the radiation of the heat treatment interval. So you can, for example the first part of the foam layer e.g. 2 minutes heat and then e.g. heat for another 4 minutes and Irradiate the opposite surface for 4 minutes. It is also conceivable that the two partial areas are e.g. 3 Heat or irradiate minutes synchronously and then the heat treatment of one partial area e.g. To continue for 2 minutes after the irradiation of the other partial area has ended Has. These treatment rhythms can also be changed if necessary while maintaining or changing the selected time intervals Repeat one or more times.
  • foamed polymerizable material can be any conventional Use imagesetter systems, provided their emission spectrum is on the photoinitiator used is adapted.
  • the polymerization by exposure is advantageously a combination a photoinitiator, a thermal initiator or / and but a photoinitator is used, which is also used as a thermal initiator can work, e.g. Azo initiators.
  • the foam settles during polymerization due to the high heat of polymerization warmed up, this makes it particularly quick and effective The polymerization reaction is complete.
  • the polymerization temperature in the range of 0 to 150, preferably 10 to 100 ° C.
  • a major advantage of the method according to the invention is to be seen in the fact that the polymerization is largely preserved the structure of the foamed polymerizable aqueous mixture expires, i.e. the polymerizable foam changes during the Polymerization its volume is insignificant.
  • the polymerization reaction is determined by the starting temperature, the initiation technique or affects the heat dissipation.
  • the polymerization temperature is preferably checked to ensure that boiling the polymerizable aqueous mixture is avoided.
  • Polymerization occurs when the foam solidifies due to increasing gel formation. At least the foam has partly an open cell structure. It is preferably too much than 75% open cell.
  • the foams present have a water content between 10% and 80%.
  • foams can be obtained, which also in dried state are flexible.
  • the foams are hygroscopic and absorb moisture from the air anyway, it makes sense to have a residual moisture in the range from 1 to 20, preferably Leave 5 - 15 wt .-% in the foam.
  • it may vary Composition of the foam and the intended area of application a different moisture content in the To leave foam.
  • the foam can be dried using conventional techniques e.g. by heating with a hot gas stream, by applying vacuum, by infrared radiation or by Heating with microwave radiation.
  • the microwave radiation again proves itself when drying large-volume ones Shaped bodies as advantageous.
  • the temperature should less than 180 ° C, preferably less than 120 ° C. It can be beneficial to be dried with a gas stream that defines a Moisture content (up to the use of water vapor), so that the foam only up to a defined way Moisture content is dried.
  • open-cell superabsorbent foam which preferably at least 75% is open cell.
  • Suitable compounds that have latent crosslinking points for example Hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, Monoacrylic acid esters of glycerol, monoacrylates or monomethacrylates of polyethylene glycols with at least 2 ethylene glycol units, Monoacrylates or monomethacrylates of polypropylene glycols with at least 2 propylene glycol units and monomethacrylates of polyhydric alcohols, e.g. hydroxybutyl, Hydroxypropyl methacrylate, hydroxyethyl methacrylate or Glycerol.
  • cross-linking reagents i.e. Compounds which have at least two reactive groups
  • the are able under suitable conditions e.g. when heating to temperatures of at least 70 ° C, with the acid groups of to react foam-like hydrogel.
  • suitable crosslinkers form with the carboxyl groups of the polymer matrix covalent or ionic bonds.
  • Suitable crosslinking agents are compounds that have at least two functional groups of the same or different types, e.g.
  • Preferred post-crosslinking agents are polyalcohols such as glycerin, butylene glycol, propylene glycol or bisepoxides. With such crosslinkers, the reaction can e.g. in the temperature range from 70 - 170, preferably at 100 - 160 ° C respectively. Applying the crosslinking agent to the foamed Material can for example by spraying, dipping or by Vapor deposition takes place.
  • the foam can be used in the usual way with a lower degree of neutralization, typically between 0 and 60%, preferably 15 to 40%, as the final intention
  • a lower degree of neutralization typically between 0 and 60%, preferably 15 to 40%
  • a solvent for alkanolamines can e.g. Find use: water, methanol, ethanol, isoPropanol, Acetone. Water is preferred.
  • the post-neutralization expediently takes place after the polymerization and before Drying.
  • Tertiary alkanolamines can - like already described above - for the neutralization of the monomers (a) are used as well as primary, secondary and quaternary alkanolamines for neutralizing the acid groups of the foam hydrogel after polymerization are used.
  • a way of working has proven to be advantageous underlined, in which the monomers containing acid groups (a) initially partially with a tertiary alkanolamine neutralized (e.g.
  • the Total degree of neutralization of the acid groups in the hydrogel 55 to 95 is preferably 65 to 85 mol%.
  • the structure of the alkanolamines used can be primarily be secondary, tertiary or quaternary and monovalent, multivalent or represent polyfunctional bases.
  • the alkanolamines can in addition to their amino and hydroxyl groups, other functional ones Groups such as Esters, urethane, ethers, thioethers, urea etc. wear. Can be used e.g.
  • low molecular weight Compounds such as triethanolamine, methyldiethanolamine, dimethylethanolamine, Ethanolamine, N-hydroxyethylmorpholine, dimethylaminodiglycol, N, N, N ', N'-tetra- (hydroxyethyl) ethylenediamine, N, N, N ', N'-tetra (hydroxypropyl) ethylenediamine, dimethylaminotriglycol, Diethylaminoethanol, 3-dimethylamino-1,2-propanediol, triisopropanolamine, Diisopropylaminoethanol, choline hydroxide, choline carbonate, 2-tert-butylaminoethanol, tris (oxymethyl) aminomethane, 3-amino-1-prooanol, isopropanolamine, 2- (2-aminoethoxy) ethanol, 2-amino-2-methyl-1-propanol or oligomeric or polymers such as e.g
  • polyethyleneimines or polyvinylamines reaction products from at least bifunctional, low molecular weight alkanolamines with at least bifunctional reagents that are able to either with the hydroxyl or the amino group of the alkanolamines to react, e.g. Carboxylic acids, esters, epoxides, isocyanates.
  • Triethanolamine methyldiethanolamine, dimethylaminodiglycol, Dimethylethanolamine, ethanolamine, N, N, N ', N'-tetra- (hydroxyethyl) ethylenediamine into consideration.
  • the alkanolamine-containing foams obtained are sticky.
  • the Tackiness can be completely eliminated by powdering with finely divided powders be eliminated.
  • all are organic or inorganic materials in fine powder form suitable, provided they are hydrophilic, e.g. finely divided silicon oxide (Aerosil®), silicates, talc, guar gum, tara gum, locust bean gum, all kinds of strengths, networked or not cross-linked polyacrylic acids or their salts, polyvinyl alcohols, Copolymers of maleic acid, titanium dioxide, zeolites, cellulose, Carboxymethyl cellulose and hydroxyechyl cellulose.
  • the powdering is expediently carried out after Polymerization can also take place at any later time be carried out in the manufacturing process.
  • the application rates are between 0.01 and 10%, preferably between 0.1 and 5%, based on the weight of the foam.
  • the superabsorbent foams according to the invention have, for example, a density of 10 -3 to 0.9, preferably 0.05 to 0.7 g / cm 3 .
  • the density of superabsorbent foams is determined gravimetrically. Squares with a side length of 5 cm are cut out of a uniform foam layer with a defined thickness between 3 and 5 mm, for example with a sharp knife. These samples are weighed and the weight obtained is divided by the volume calculated from the measurements.
  • the absorption capacity of the foam-like superabsorbent of water per gram of superabsorbent is determined on pieces of foam which have a thickness of 3 mm and each weigh 1 g.
  • the retention is checked according to the so-called teabag test.
  • a 0.9% saline solution serves as the liquid, 1 g of the foam-like material is poured into a tea bag, which is then sealed. Make sure that the tea bag offers enough space to swell completely. The tea bag is then immersed in the liquid for a certain time and weighed back after 10 minutes of draining.
  • the absorption speed (hereinafter referred to as AS) was determined by cutting out rectangular samples with a weight of 1 g from a uniformly 3 mm thick foam layer using a sharp knife. 20 g of synthetic urine were poured over these samples in a Petri dish. A stopwatch was used to determine the time it took for the foam to completely absorb the synthetic urine.
  • the salts used must be anhydrous.
  • Exactly 100 ml of the monomer foam are poured into a measuring cylinder and the weight of this foam volume is determined.
  • the density in g / cm 3 is obtained by dividing the determined weight in g by 100.
  • Each foam is about 2 cm x 2 cm, dried pieces introduced into these chambers and the change in moisture content followed gravimetrically in the foams until the samples Have reached equilibrium.
  • the water-absorbent, foam-like, cross-linked described above Polymers can be used for all purposes for the foam-like ones described in the literature Superabsorbers are used. You will e.g. in sanitary ware, which are used to adsorb body fluids and used in dressing materials to cover wounds. They are suitable, for example, as a water-absorbing component in diapers, sanitary napkins and incontinence articles. You can be used in the form of composite materials. foam shaped Superabsorbents can also be used as sealing materials, as soil improvers, as a soil substitute and as packaging material be used. Special designs of objects, which contain foam-like superabsorbents, for example described in detail in WO-A-94/22502.
  • the foam-like Superabsorbents are also suitable for dewatering Slurries, for thickening aqueous paints, e.g. for disposal of residual amounts of unused aqueous paints or inks, e.g. by powdery foam superabsorbents too adds aqueous paint residues until solidification occurs.
  • the foam-like, water-absorbing, crosslinked polymers can also be used to drain water-containing oils become. You can, for example, in the form of a powder an average particle diameter of 150 ⁇ m to 5 mm in the Applications described above can be used.
  • the storage of body fluids is done by the foams fully undertaken while for the acquisition functions and distribution, if necessary, other components such as high loft nonwovens, polypropylene nonwovens, polyester nonwovens or chemically modified cellulose as a layer the foams can be used.
  • the homogeneous mixture obtained was placed in a closed 2 1 flask filled with cooling jacket and dropping funnel, in the of carbon dioxide was introduced below. There were two in the flask Whisk from BOKU is used, which has a gearbox a RW28W stirrer from IKA were connected.
  • the carbon dioxide flow was set to run at a speed of 100 l / h bubbled through the reaction mixture.
  • the stirring motor was initially set to a speed of 200 rpm and passed carbon dioxide through the mixture for 20 min to be dissolved Remove oxygen. During this time, 140.26 g Triethanolamine (0.94 mol) was added dropwise with cooling so that a Final temperature of 16 ° C was reached.
  • the monomer foam obtained was placed on a DIN A3 glass plate applied with 3 mm high edges and with a second Glass plate covered.
  • the foam sample was synchronized by both Sides with two UV / VIS lamps (UV 1000 from Höhnle) for 4 Irradiated minutes.
  • the foam layer obtained was powdered on both sides with about 0.3 g of talc and completely dried in a vacuum drying cabinet at 70.degree. To determine the properties, part of the foam was then adjusted to a moisture content of 10% by spraying with water. Degree of neutralization 75 mol% Monomer 0.33 g / cm 3 Polymer foam density 0.44 g / cm 3 Handle dry, completely tack-free
  • the homogeneous mixture obtained was placed in a closed 2 1 flask filled with cooling jacket, in the carbon dioxide from below was initiated. There were two whisks in the flask
  • the BOKU company used a gearbox with a stirrer RW28 W of the company IKA were connected.
  • the carbon dioxide stream was set so that it runs at a speed of 100 l / h bubbles through the reaction mixture.
  • the stirring motor was initially set to a speed of 200 rpm and carbon dioxide for 20 min passed through the mixture to dissolved oxygen remove. During this time, the indoor temperature became too Cooled to 16 ° C with the help of the cooling jacket and a thermostat.
  • the monomer foam obtained was placed on a DIN A3 glass plate applied with 3 mm high edges and with a second glass plate covered.
  • the foam sample was then synchronized by both sides with two UV / VIS lamps (UV 1000 from Höhnle) irradiated for 4 minutes.
  • the foam layer obtained was powdered on both sides with about 0.3 g of talc and completely dried in a vacuum drying cabinet at 70.degree. To determine the properties, part of the foam was then adjusted to a moisture content of 10% by spraying with water. Degree of neutralization 45.0 mol% Monomer 0.29 g / cm 3 Polymer foam density 0.35 g / cm 3 Handle dry, completely tack-free
  • a foam was produced starting from the following starting materials: 33.01 g Acrylic acid (0.46 mol) 379.98 g a 40.0% triethanolammonium acrylate solution in water (0.69 mol) 9.25 g guar Gum 1.85 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 600 12.33 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 72.83 g water 4.63 g pentane 20.97 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water Degree of neutralization 60 mol% Monomer 0.30 Polymer foam density 0.40 Handle dry, completely tack-free
  • a foam was made from the following starting materials: 22.66 g Acrylic acid (0.31 mol) 405.84 g a 40.0% triethanolammonium acrylate solution in water (0.73 mol) 9.25 g guar Gum 1.85 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 650 12.33 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 57.31 g water 4.63 g pentane 20.97 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water Degree of neutralization 70 mol% Monomer 0.32 Polymer foam density 0.50 Handle dry, completely tack-free
  • the homogeneous mixture obtained was placed in a closed 2 1 flask filled with cooling jacket, in the carbon dioxide from below was initiated. There were two whisks in the flask
  • the BOKU company used a gearbox with a stirrer RW28 w were connected to the IKA company.
  • the carbon dioxide stream was set so that it runs at a speed of 100 l / h bubbled through the reaction mixture.
  • the stirring motor was initially set to a speed of 200 rpm and carbon dioxide for 20 min passed through the mixture to dissolved oxygen remove. During this time, the indoor temperature became too Cooled to 16 ° C with the help of the cooling jacket and a thermostat.
  • the monomer foam obtained was placed on a Din A3 glass plate applied with 3 mm high edges and with a second glass plate covered.
  • the foam sample was synchronized from both sides with two UV / VIS lamps (UV 1000 from Höhnle) for 4 minutes irradiated.
  • the foam layer obtained was sprayed with a 10% strength aqueous triethanolamine solution, so that the degree of neutralization was increased from 30 mol% to 75 mol% and then powdered on both sides with about 0.3 g of talc.
  • the foam was completely dried in a vacuum drying cabinet at 70 ° C. To determine the properties, part of the foam was then adjusted to a moisture content of 10% by spraying with water.
  • Degree of neutralization 75 mol% Monomer 0.34 g / cm 3 Polymer foam density 0.39 g / cm 3 Handle dry, completely tack-free
  • the homogeneous mixture obtained was placed in a closed 2 1 flask filled with cooling jacket and dropping funnel, in the of nitrogen was introduced below. There were two in the flask Whisk from BOKU is used, which has a gearbox a RW28 W stirrer from IKA were connected.
  • the nitrogen flow was set to run at a speed of 100 l / h bubbled through the reaction mixture.
  • the stirring motor was initially set to a speed of 200 rpm and for 20 min nitrogen passed through the mixture to dissolved oxygen to remove. During this time, 124.53 g of methyldiethanolamine (1.05 mol) added dropwise with cooling so that a final temperature of 16 ° C was reached.
  • the monomer foam obtained was cut into a 20 cm x 20 cm Teflon-coated aluminum mold with a 3 mm high edge filled and covered with a glass plate.
  • the shape was made for 2 min on a heating plate (Ceran 500) with a surface temperature of 115 ° C, then simultaneously for 2 min from exposed above with a UV / VIS radiator (UV 2000 from Höhnle) and further heated from below and finally without for 2 min Leave the exposure on the heating plate.
  • the foam layer obtained was powdered on both sides with about 0.3 g of talc and completely dried in a vacuum drying cabinet at 70.degree. To determine the properties, part of the foam was then adjusted to a moisture content of 10% by spraying with water. Degree of neutralization 75 mol% Monomer 0.36 g / cm 3 Polymer foam density 0.43 g / cm 3 Handle dry, completely tack-free
  • a foam was produced starting from the following starting materials: 120.18 g Acrylic acid (1.67 mol) 105.13 g a 37.3% sodium acrylate solution in water (0.42 mol) 12.60 g guar Gum 8.82 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 600 58.78 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 55.99 g water 155.51 g Triethanolamine (1.04 mol) 4.63 g pentane 20.99 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water
  • a foam was produced starting from the following starting materials: 127.93 g Acrylic acid (1.77 mol) 93.43 g a 37.3% sodium acrylate solution in water (0.37 mol) 12.60 g guar Gum 6.29 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 400 58.78 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 63.02 g water 152.42 g Triethanolamine (1.02 mol) 4.63 g pentane 20.99 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water
  • a foam was produced starting from the following starting materials: 140.44 g Acrylic acid (1.95 mol) 12.60 g guar Gum 8.81 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 600 58.78 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 121.60 g water 174.46 g Triethanolamine (1.17 mol) 4.63 g pentane 20.99 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water
  • the homogeneous mixture obtained was placed in a closed 2 1 flask filled with cooling jacket, in the carbon dioxide from below was initiated. There were two whisks in the flask
  • the BOKU company used a gearbox with a stirrer RW28 W of the company IKA were connected.
  • the carbon dioxide stream was set so that it runs at a speed of 100 l / h bubbled through the reaction mixture.
  • the stirring motor was initially set to a speed of 200 rpm and carbon dioxide for 20 min passed through the mixture to remove dissolved oxygen. During this time the inside temperature was using of the cooling jacket and a thermostat set to 16 ° C.
  • the monomer foam was placed on a DIN-A3 glass plate with 3 mm high edges and covered with a second glass plate.
  • the foam sample was synchronized from both sides with two UV / VIS lamp (UV 1000 from Höhnle) irradiated for 4 minutes.
  • the foam layer obtained was completely dried in a vacuum drying cabinet at 70 ° C. and then adjusted to a moisture content of 25% by spraying with water. Degree of neutralization 75 mol% Monomer 0.31 g / cm 3 Polymer foam density 0.32 g / cm 3 Handle moist, hardly sticky
  • a foam was produced using the same procedure as in Comparative Example 1, starting from the following components: 83.51 g Acrylic acid (1.16 mol) 292.28 g a 37.3% sodium acrylate solution in water (1.16 mol) 9.25 g guar Gum 1.85 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 500 58.58 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 69.55 g water 4.63 g pentane 20.97 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water Degree of neutralization 50 mol% Monomer 0.26 g / cm 3 Polymer foam density 0.29 g / cm 3 Handle moist, hardly sticky
  • a foam was produced using the same procedure as in Comparative Example 1, starting from the following components: 116.90 g Acrylic acid (1.62 mol) 175.37 g a 37.3% sodium acrylate solution in water (0.70 mol) 9.25 g guar Gum 6.48 g Polyethylene glycol diacrylate of a polyethylene glycol with a molecular weight of 500 58.58 g a 15% aqueous solution of an addition product of 80 moles of ethylene oxide with 1 mole of a linear, saturated C 16 C 18 fatty alcohol 144.79 g water 4.63 g pentane 20.97 g a 3% solution of 2,2'-azobis (2-amidinopropane) dihydrochloride in water Degree of neutralization 30 mol% Monomer 0.26 g / cm 3 Polymer foam density 0.24 g / cm 3 Handle moist, hardly sticky
  • Teflon plates were placed in a 50 ° C water bath.
  • Teflon plates were placed in a 50 ° C water bath.
  • the gel film obtained was in a vacuum drying cabinet at 70 ° C. completely dried and then in a polyethylene bag with the necessary amount of water added to a residual moisture content in the gel set by 10% and welded. After a Waiting time of 10 days, the gel layer was moistened evenly.
  • Teflon plates were placed in a 50 ° C water bath.

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Claims (9)

  1. Polymères réticulés hygroscopiques sous forme de mousse que l'on peut obtenir
    (I) en faisant mousser un mélange aqueux polymérisable qui contient
    (a) des monomères à insaturation monoéthylénique contenant des groupes acides, qui ont éventuellement été neutralisés,
    (b) éventuellement d'autres monomères à insaturation monoéthylénique,
    (c) des agents réticulants,
    (d) des amorceurs,
    (e) 0,1% à 20% en poids d'au moins un tensio-actif,
    (f) éventuellement au moins un solubilisant et
    (g) éventuellement des épaississants, des stabilisants de mousse, des régulateurs de polymérisation, des charges et/ou des agents nucléants,
    le moussage étant réalisé en dispersant de fines bulles d'un gaz inerte envers les radicaux libres dans le mélange aqueux polymérisable, et
    (II) en polymérisant le mélange expansé en formant un hydrogel sous forme de mousse et éventuellement en ajustant la teneur en eau du polymère sous forme de mousse à une valeur allant de 1% à 60% en poids, caractérisés en ce qu'au moins 20% en moles des monomères (a) contenant des groupes acides ont été neutralisés avec des alcanolamines tertiaires et/ou en ce qu'au moins 20% en moles des groupes acides libres de l'hydrogel sous forme de mousse ont été neutralisés après la polymérisation avec au moins une alcanolamine.
  2. Polymères réticulés hygroscopiques sous forme de mousse selon la revendication 1, caractérisés en ce qu'au moins 40% en moles des monomères (a) contenant des groupes acides ont été neutralisés avec des alcanolamines tertiaires.
  3. Polymères réticulés hygroscopiques sous forme de mousse selon la revendication 1, caractérisés en ce qu'au moins 40% en moles des groupes acides des hydrogels sous forme de mousse ont été neutralisés avec au moins une alcanolamine, la neutralisation ayant été réalisée une fois la polymérisation achevée.
  4. Polymères réticulés hygroscopiques sous forme de mousse selon la revendication 2, caractérisés en ce que les alcanolamines sont choisies dans le groupe formé par la triéthanolamine, la méthyldiéthanolamine, le diméthylaminodiglycol, la diméthyléthanolamine et la N,N,N',N'-tétra(hydroxyéthyl)éthylènediamine.
  5. Procédé de préparation de polymères réticulés hygroscopiques sous forme de mousse, dans lequel on fait mousser, dans une première étape de procédé, un mélange polymérisable composé
    (a) de monomères à insaturation monoéthylénique contenant des groupes acides, qui ont éventuellement été neutralisés,
    (b) éventuellement d'autres monomères à insaturation monoéthylénique,
    (c) d'agents réticulants,
    (d) éventuellement au moins un amorceur de polymérisation,
    (e) 0,1% à 20% en poids d'au moins un tensio-actif,
    (f) éventuellement au moins un solubilisant et
    (g) éventuellement des épaississants, des stabilisants de mousse, des régulateurs de polymérisation, des charges et/ou des agents nucléants,
    en dispersant de fines bulles d'un gaz inerte envers les radicaux libres et, dans une deuxième étape de procédé, en polymérisant la mousse ainsi obtenue en formant un hydrogel sous forme de mousse et éventuellement en ajustant la teneur en eau du polymère sous forme de mousse à une valeur allant de 1% à 60% en poids, caractérisé en ce que l'on neutralise au moins 20% en moles des monomères (a) contenant des groupes acides avec des alcanolamines tertiaires et/ou en ce que l'on neutralise après la polymérisation au moins 20% en moles des groupes acides libres de l'hydrogel sous forme de mousse avec au moins une alcanolamine.
  6. Procédé selon la revendication 5, caractérisé en ce que les alcanolamines sont choisies dans le groupe formé par la triéthanolamine, la méthyldiéthanolamine, le diméthylaminodiglycol, la diméthyléthanolamine, l'éthanolamine et la N,N,N',N'-tétra(hydroxyéthyl)éthylènediamine.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce que l'on neutralise au moins 40% en moles des monomères (a) contenant des groupes acides avec des alcanolamines tertiaires et/ou en ce que l'on neutralise après la polymérisation au moins 40% en moles des groupes acides libres de l'hydrogel sous forme de mousse avec au moins une alcanolamine.
  8. Utilisation des polymères réticulés hygroscopiques sous forme de mousse selon l'une quelconque des revendications 1 à 4 ou pouvant être obtenus selon un procédé des revendications 5 à 7 dans des articles hygiéniques qui sont mis en oeuvre pour absorber des liquides corporels, dans des matériaux de pansement pour le recouvrement de plaies, en tant que matériaux d'étanchéité, en tant qu'agents d'amendement des sols, en tant que substituts de sol et en tant que matériaux d'emballage.
  9. Utilisation des polymères réticulés hygroscopiques sous forme de mousse selon l'une quelconque des revendications 1 à 4 ou pouvant être obtenus selon un procédé des revendications 5 à 7 sous la forme d'une poudre ayant une granulométrie moyenne de 150 µm à 5 mm dans des articles hygiéniques qui sont mis en oeuvre pour absorber des liquides corporels, dans des matériaux de pansement pour le recouvrement de plaies, en tant que matériaux d'étanchéité, en tant qu'agents d'amendement des sols et en tant que substituts de sol pour la culture de plantes.
EP99913215A 1998-03-05 1999-03-03 Polymerisats absorbant l'eau, sous forme de mousse, reticules, leur procede de production et leur utilisation Expired - Lifetime EP1059947B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19809540 1998-03-05
DE19809540A DE19809540A1 (de) 1998-03-05 1998-03-05 Wasserabsorbierende, schaumförmige, vernetzte Polymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP1999/001363 WO1999044648A1 (fr) 1998-03-05 1999-03-03 Polymerisats absorbant l'eau, sous forme de mousse, reticules, leur procede de production et leur utilisation

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US6455600B1 (en) 2002-09-24
EP1059947A1 (fr) 2000-12-20
DE59910656D1 (de) 2004-11-04
DE19809540A1 (de) 1999-09-09
JP2002505348A (ja) 2002-02-19
JP4204196B2 (ja) 2009-01-07
ES2228027T3 (es) 2005-04-01
WO1999044648A1 (fr) 1999-09-10

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